Certain triazolo-naphthoquinone compounds



E ir hates tent fi Fatenteel Aug". 3, 1955 3,198,75TRIAZCLQ-WAPHTHGQU1NGNE CGIVEEGUNDES Wiliisrn Lindsay Mosby, NorthPlainfieid, and Mary- Lonise Silva, Somerviile, Ni, assiguors toAmerican Cyanamid Company, Stamford, Conn, a corporation of Maine NoFiled May 2, 1953, Ser. No. 277,469 4 (12352235. (Cl. Edd-$47.5)

This invention relates to, and has for its object, the provision of anew class of compounds which may be termed 2amino-4,9-dihydro-4,9-dioXo-2il-naphtho[2,3- d]triazoles. It relatesfurther to the novel method by which these paraquinoidal aminotriazoiesare prepared, viz: The hydrolysis of the corresponding phosphine imides,which latter also constitute a new class of compounds. It relates stillfurther to the preparation of said phosphine irnides by a method whichinvolves treating a vicinal diazido-paraquinone with a member of acertain class of trivalent phosphorous reagents. The invention will bebetter understood if reference is made to the following detaileddescription taken in conjunction with the examples showing practice ofall the aspects thereof. The Z-amino-triazolo-paraquinones of thepresent in vention may be represented by the following general formula:

In this formula, the X, X X and X symbols are individually intended torepresent either hydrogen, halogen (e.g., fluorine, chlorine, bromineand iodine, especially chlorine and bromine), alkyl (especially loweralkyl such as methyl, ethyl, butyl, hexyl, cyclohexyl and heptyl),alkoxy (especially lower alkoxy such as methoxy, ethoxy. and amyloxy),amino, alkanarnido (e.g., lower allianarnido) and nitro.

The novel reaction leading to the formation of compounds of Formula I isgraphically represented by the following general Equation A:

I II N X1 I II N X3 0 wherein X, X X and X are as defined above, and R,R and R are individually intended to represent either lower alkyl,monocyclic aryl (e.g., phenyl and tolyl), monocyclic ar(lower alkyl),di- (lower alkyl) amino, merpholino, piperidino or piperazino.

The hydrolysis of Compound II is preferably conducted in water in thepresence of a strong acid, e.g., hydrochloric, hydrobrornic, sulfuric,phosphoric, nitric, etc. Normally elevated temperatures, up to reflux,are required for the reaction to proceed at a reasonable rate. A polarsolvent such as aqueous acetic acid may be employed, but is notnecessary. The product, obtained as a colored precipitate, may beseparated by filtration and purified by conventional crystallizationtechniques.

Compounds of Formula I are water-insoluble colored solids, and they arethus useful as pigments or as colorants for plastics.

The phosphoranylideneamino triazolo-paraquinones of Formula 11, servingas starting materials in the preparation of Compound I, are themselvesnew compounds, obtained by the reaction of an aryl phosphine, an alkylphosphine, aryl phosphonous diamides, diaryl phosphinous amides or aphosphorous triamide with a vicinal diazidoparaquinone. I

This novel reaction is graphically represented by the following generalEquation B:

wherein X, X X X R, R and R are as defined above.

The reaction is carried out in an inert solvent such as toluene,methylene chloride, ethyl acetate, ethylene chloride, benzene,chloroform, chlorobenzene, diethyl ether, dibutyl ether, carbontetrachloride, nitromethane, etc.

The reaction temperature may be between 20 and 200 C. Normally it isadvantageous to carry out the reaction at the reflux temperature of thereaction mixture.

By theory, equivalent amounts of diazido-paraquinone and the phosphorousreagent are required. However, either reactant may be used in slightexcess. 7

The desired phosphoranylideneamino-triazoles may be obtained in the formof colored precipitates. They may be separated from their respectivereaction mixtures by filtration, or they can be obtained by evaporatingthe solvent from the reaction mixture. They can then be purified byconventional recrystallization techniques. They are useful as pigments.

Among the diazido-paraquinones which may be reacted as in Equation B arethe following: 2,3-diazido-1,4- naphthoquinone, 2,3 diazido 5 methyl 1,4naphthoquinone, 2,3 diazido-S-nitro 1,4 napthoquinone, 2,3-diazido-5,8-dichloro-l,4-naphthoquinone and 2,3-diazido-5,6,7,8-tetrachloro-1,4-naphthoquinone.

These diazido-paraquinones are generally obtainable by the reaction ofthe corresponding 2,3-dihalo-L 4- naphthoquinone with two moles of analkali metal azide (e.g., sodium azide). This reaction is conducted in asolvent medium such as dimethylformamide. After about 15 minutes to onehour, the diazido-paraquinone may be isolated by dilution with water andfiltration.

Among the alkyl phosphines which may be employed in Reaction A are thelower alkyl phosphines such as trirnethylphosphine, triethylphosphineand tributylphosphine.

Among the triaryl phosphines which may be used are triphenylphosphine,the trito'lylphosphines, such as tri-otolylphosphine, thecholorophenylphosphines, such as tris(4-chlorophenyl)phosphine, thealkoxyphenylphosphines, such as tris(Z-methoxyphenyl)phosphine,trinaphthylphosphines, and also mixed triaryl phosphines, such asdiphenyl p tolylphosphine, diphenyl-4-methoxyphenylphosphine, dipenyl 4chlorophenylphosphine, phenylbis-p-tolylphosphine, 4-chlorophenyl-bis ptolylphosphine.

The phosphorous triamides which may be used include phosphoroustripiperidide, phosphorous trimorpholide,N,N,N',N,N,N-hexaethylphosphorous triamide, N,N,N',N',N",N"-hexaisopropylphosphorous triamide.

As will be obvious from the foregoing description, other trivalentderivatives of phosphorous are useful herein. Thus, fully substitutedderivatives of phosphonous diamide (viz: compounds having two aminogroups and one aryl group on the phosphorous atom) and phosphinous amide(viz: compounds having one amino group and two aryl groups on thephosphorous atom) may also be employed. Examples of useful phosphonousdiamides and phosphinous amides are N,N,N',N'-tetraethyl-P-phenylphosphonous diamide and N,N diethyl P,P diphenylphosphinousamides, respectively.

The following examples are presented to further illustrate the presentinvention.

Example 1 A solution of 2.75 parts (0.0105 mole) of triphenylphosphinein parts of toluene is added slowly to a solution of 1.20 parts (0.005mole) of 2,3-diazido-1,4- naphthoquinone in 40 parts of toluene at -25C. After heating at the boil until the evolution of gas ceases, thereaction'mixture is cooled and the precipitate is removed by filtration.Crystallization from benzene removes a blue by-product, leaving yellow,crystalline material melting at 252-253 C.

Example 2 c1 0 [I N \N-N=P (C5115) 3 01- To a suspension of 0.756 part(0.002 mole) of 2,3- diazido-5,6,7,S-tetrachloro 1,4 naphthoquinone in300 parts of methylene chloride there is added 1.15 parts (0.0044 mole)of triphenylphosphine. The reaction mixture is refluxed for aboutminutes, followed by evaporation of most of the solvent. From theremaining solution there may be separated a scarlet, crystalline productwhich melts at 294-295 C.

Example 3 A solution of 2.01 parts (0.0071 mole) of phosphoroustripiperidide in 15 part of methylene chloride is added slowly to asolution of 0.60 part (0.0025 mole) of 2,3- diazido-1,4-naphthoquinonein parts of methylene chloride. After the reaction mixture is refluxedfor about 30 minutes, the methylene chloride is evaporated and theresidue is dissolved in benzene. From the benzene solution there isseparated a red product, which, after recrystallization, melts at l69170C.

Example 4 O H N NN=I| N 1| N O A solution of 6.90 parts (0.025 mole) ofphenylphosphonous dipiperidide in about 15 parts of methylene chlorideis slowly added to a solution of 2.40 parts (0.01 M) of2,3-diazido-1,4-naphthoquinone in about parts of methylene chloride atambient temperature. When the reaction is completed, the solvent ispartially evaporated and the precipitate is separated by filtration,washed with benzene, then with petroleum ether and dried. Theorange-colored product, after recrystallization from benzene and fromethyl acetate, melts at 212.5-2l3.5 C.

Example 5 A solution of 4.40 parts of tri-n-butylphosphine in about 15parts of methylene chloride is added slowly to a solution of 2.40 partsof 2,3-diazido-1,4-napthoquinone in about 135 parts of methylenechloride at ambient ternperature. The solvent is removed by evaporationand the red residue is chromatographically fractionated on a column ofalumina using benzene as the solvent and eluting liquid. The redfraction is taken up in hexane, and the solution is filtered andevaporated. The red product melts at 76.578.0 C.

Example 6 I! N W a\ III N NHZO A solution of 2.80 parts oftriphenylphosphine in about 15 parts of methylene chloride is slowlyadded to a solution of 1.32 parts of5-amino-2,3-diazido-l,4-naphthoquinone in about 30 parts of methylenechloride at ambient temperature. When the reaction is finished, thesolvent is evaporated, and the residue is washed with cyclohexane andthen with petroleum ether and dried. Extraction with benzene leaves ared-brown material which is crystallized from nitromethane. The productmelts at 253.5-254.5 C.

Example 7 i 6 ethyl acetate and petroleum ether, extraction withbenwherein X, X X and X are individually selected from zene, andrecrystallization from nitromethane, melts at the group consisting ofhydrogen, halogen, lower alkyl, 264.6265.0 C. lower alkoxy, amino andnitro radicals, no more than Example 8 one X being amino and no morethan one X being 5 nitro in any instance; and II N R, R and R areindividually intended to represent lower alkyl, phenyl, tolyl,chlorophenyl, methoxyphenyl,

N N:P(CfiH5)3 naphthyl, di-(lower alkyl)amino, morpholino, pyrrolidino,piperidino and piperazino moieties. H 3. A compound having the formula:l ro o A solution of 5.80 parts of triphenylphosphine in about 6 10parts of benzene is added slowly to a suspension of R 2.91 parts of2,3-diazido-5-nitro-1,4-naphthoquinone in about 90 parts of benzene atambient temperature. The I N=P R1 reaction is continued until themixture becomes green. R2 The solvent is partially evaporated, and theresidual solul I; N

tion, when cooled, deposits red crystals which are separated from thegreen solution by filtration. The prodnot, after recrystallization fromnitromethane, melts at Wnerfim X2 and X3 are mdmduauy selected from thegroup consisting of hydrogen, halogen, lower alkyl, Example 9 loweralkoxy, amino, lower alkanamido and nitro 0 radicals, no more than one Xbeing amino and no N N more than one X being nitro in any instance; and

R, R and R are individually intended to represent lower I N NH alkyl,phenyl, tolyl, chlorophenyl, methoxyphenyl, naphthyl, GI-(lOWClalkyl)am1no, morphollno, pyrrohdino, piperidino and piperazino moieties.

A mixture of one part of the product of Example 1,

40 parts of glacial acetic acid, 3 parts of concentrated f i? Nhydrochloric acid and 3 parts of water is boiled for five R minutes,then diluted with a large volume of water. Filtration yields a yellowsolid, M. 313-4 dec. It may be X1 1 crystallized from hot pyridine. R:

We claim: H "a. A compound having the formula: 2

N 40 which comprises contacting a compound having the formula: .Xr-

l N-NHz X2- X I l I N X3 0 1- N3 wherein X, X X and X are individuallyselected from the group consisting of hydrogen, halogen, lower alkyl, XN3 lower alkoxy, amino and nitro radicals; no more than I ll one X beingamino and no more than one X being nitro 0 in any instance.

2. A process which comprises hydrolyzing a compound with a trivalentphosphorous compound of the formula: having the formula:

| l N PR1 X1- /R R2 NN=PR1 XV and recovering the triazole thus formed;

I H N wherein X, X X and X are individually selected from X 0 0 thegroup consisting of hydrogen, halogen, lower alkyl, said hydrolysisbeing effected at an elevated temperature, lower y, amino, loweralkaflamido d llitlo up to reflux temperature, in an aqueous solution ofa radicals, more than 0116 X being amino and 110 more strong acid; andrecovering from the reaction product a than 0116 X being IlilirO in yinstance; and compound having the formula: R, R and R are individuallyintended to represent lower X o alkyl, phenyl, tolyl, chlorophenyl,methoxyphenyl, I II N naphthyl, di- (lower alkyl)amino, morpholino,pyrroli- X dino, piperidino and piperazino moieties.

N-NH: X No references cited.

N 0 X3 NICHOLAS S. RIZZO, Primary Examiner.

4. A process of preparing a triazole having the formula:,

1. A COMPOUND HAVING THE FORMULA:
 3. A COMPOUND HAVING THE FORMULA: